Water soluble containers and methods of making them

ABSTRACT

A water soluble container comprises a water soluble shell enclosing a volume. The water soluble shell comprises a set of voxels.

FIELD OF THE INVENTION

The invention relates to water soluble containers. The invention relatesparticularly to water soluble containers containing an active or benefitagent.

BACKGROUND OF THE INVENTION

The use of active agents in solution to achieve desired outcomes is wellknown. Cleaning, disinfecting, conditioning and other agents aresolubilized to provide better efficacy by distributing the agentsthroughout the solution enabling contact and action upon any targetitems placed in the solution. Achieving the proper dosing of respectiveactive agents, in addition to achieving the desired release of theagents into solution in terms of both timing and agent sequence ischallenging. What is needed is a mechanism to enable proper dosing andrelease of active agents in liquid environments for the purpose ofhaving the agent act upon target objects in contact with theenvironment.

SUMMARY OF THE INVENTION

In one aspect, a water soluble container comprises a water soluble shellenclosing a volume, the shell comprising a set of voxels.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a schematic illustration of one embodiment of theinvention.

FIG. 2 provides a schematic illustration of a second embodiment of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise noted, all composition percentages are provided as % byweight

In one embodiment, a water soluble container comprises a water solubleshell enclosing a volume, the shell comprising a set of voxels. Theenclosed volume may be at least partially filled with an active element.The active element may comprise a solid, liquid, gaseous or multiphasecomposition.

In one embodiment, the active element may be selected from the groupconsisting of: personal cleansing and/or conditioning agents such ashair care agents such as shampoo agents and/or hair colorant agents,hair conditioning agents, skin care agents, sunscreen agents, and skinconditioning agents; laundry care and/or conditioning agents such asfabric care agents, fabric conditioning agents, fabric softening agents,fabric anti-wrinkling agents, fabric care anti-static agents, fabriccare stain removal agents, soil release agents, dispersing agents, sudssuppressing agents, suds boosting agents, anti-foam agents, and fabricrefreshing agents; hard surface care agents, and/or conditioning agentssuch as liquid and/or powder dishwashing agents (for hand dishwashingand/or automatic dishwashing machine applications), and polishingagents; other cleaning and/or conditioning agents such as antimicrobialagents, perfume, bleaching agents (such as oxygen bleaching agents,hydrogen peroxide, percarbonate bleaching agents, perborate bleachingagents, chlorine bleaching agents), bleach activating agents, chelatingagents, builders, lotions, brightening agents, air care agents, carpetcare agents, water-softening agents, water-hardening agents, pHadjusting agents, enzymes, flocculating agents, effervescent agents,preservatives, cosmetic agents, make-up removal agents, latheringagents, deposition aid agents, coacervate-forming agents, clays,thickening agents, latexes, silicas, drying agents, odor control agents,antiperspirant agents, cooling agents, warming agents, absorbent gelagents, anti-inflammatory agents, dyes, pigments, acids, and bases;liquid treatment active agents; agricultural active agents; industrialactive agents; water-treatment agents such as water clarifying and/orwater disinfecting agents, and combinations thereof.

One or more classes of chemicals may be useful for one or more of theactive agents listed above. For example, surfactants may be used for anynumber of the active agents described above. Likewise, bleaching agentsmay be used for fabric care, hard surface cleaning, dishwashing and eventeeth whitening. Therefore, one of ordinary skill in the art willappreciate that the active agents will be selected based upon thedesired intended use of the particle.

In an embodiment, suitable surfactants may include anionic, nonionic,zwitterionic/amphoteric surfactants, and combinations thereof.

Suitable anionic surfactants useful herein may include, but are notlimiting to, a sulfate detersive surfactant, e.g., alkoxylated ornon-alkoxylated alkyl sulfates; a sulfonic detersive surfactant, e.g.,alkyl benzene sulfonates, paraffin sulfonates or secondary alkanesulfonates; and combinations thereof.

Suitable nonionic surfactants useful herein may include, but are notlimiting to, linear or branched alkoxylated fatty alcohols, andcombinations thereof.

Suitable cationic surfactants useful herein may include, but are notlimiting to, quaternary ammonium surfactants, cationic estersurfactants, alkyl pyridinium compounds, alkyl quaternary ammoniumcompounds, alkyl quaternary phosphonium compounds, alkyl ternarysulphonium compounds, and combinations thereof.

Suitable zwitterionic/amphoteric surfactants useful herein may include,but are not limiting to, derivatives of secondary and tertiary amines,derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Examples of zwitterionic/amphoteric surfactants maybe amine oxide or betaine surfactant.

Suitable fluorescent brighteners include: di-styryl biphenyl compounds,e.g. Tinopal® CBS-X, di-amino stilbene di-sulfonic acid compounds, e.g.Tinopal® DMS pure Xtra and Blankophor® HRH, and Pyrazoline compounds,e.g. Blankophor® SN, and coumarin compounds, e.g. Tinopal® SWN.Preferred brighteners are: sodium 2(4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium4,4′-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl)amino1,3,5-triazin-2-yl)]; amino}stilbene-2-2′ disulfonate, disodium4,4′-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2′disulfonate, and disodium 4,4′-bis(2-sulfostyryl)biphenyl. A suitablefluorescent brightener is C.I. Fluorescent Brightener 260, which may beused in its beta or alpha crystalline forms, or a mixture of theseforms.

Preferred chelants are selected from: diethylene triamine pentaacetate,diethylene triamine penta(methyl phosphonic acid), ethylenediamine-N′N′-disuccinic acid, ethylene diamine tetraacetate, ethylenediamine tetra(methylene phosphonic acid) and hydroxyethane di(methylenephosphonic acid). A preferred chelant is ethylenediamine-N′N′-disuccinic acid and/or hydroxyethane diphosphonic acid.

Suitable hueing agents include small molecule dyes, typically fallinginto the Colour Index (C.I.) classifications of Acid, Direct, Basic,Reactive or hydrolyzed Reactive, Solvent or Disperse dyes for examplethat are classified as Blue, Violet, Red, Green or Black, and providethe desired shade either alone or in combination. Preferred hueingagents include Acid Violet 50, Direct Violet 9, 66 and 99, SolventViolet 13 and any combination thereof. Suitable hueing agents includephthalocyanine and azo dye conjugates, such as described inWO2009/069077.

The active agent may comprise a single described agent or a combinationof described agents.

The container shell comprises a set of voxels or voxel elements. The setof voxels may be sequentially fabricated using fused deposition material(FDM) techniques. This involves melting the material of interest,depositing it as a set of voxels and allowing the voxels to cool andharden. The set of voxels may be provided as digital information file.Exemplary file formats include: .STL, .OBJ, G-code, SVG files, .dxffiles, and other file formats as described in ASTM F2792. The containeris preferably sealed such that the active agent is fully enclosed. Inone embodiment, the container is comprised exclusively of a series ofvoxels. In another embodiment, the container is comprised of a series ofvoxels and a sealing component. Examples of suitable sealing componentsinclude films, caps and welded polymer. In another embodiment, themajority of the container is made by traditional manufacturing methodsincluding but not limited to injection and blow molding and sealed witha series of voxels. In one embodiment, the temperature of the activeelement is similar to the printing temperature of the voxel material. Inyet another embodiment, the active element temperature is between 5 and50 C below the printing temperature of the voxel material.

The thickness of the shell may be uniform or may vary as desired.Varying the thickness may enable variations in the dissolution time forparticular portions of the shell and an accompanying variation in theexposure of the respective active elements to the environmentsurrounding the container. The water soluble shell may comprise one ofmore benefit agents within the shell itself. Such benefit agents may bereleased into the environment as the shell is solubilized.

The container may be post processed to improve the look, feel and/orfunction of the container. Examples of suitable post-processing stepsinclude sanding, painting, chemical vapor smoothing, printing and shrinkwarping.

The shape of the container may be used to convey an intended purpose oruse of the container and active elements contained within. In oneexample, the active element is a laundry detergent composition designedfor bleaching whites and the container is shaped like a white dressshirt. In another example, the composition is tailored to a specificusers needs and the container is shaped into that individuals name.

Exemplary benefit agents include: perfumes, pro-perfumes, finishingaids, malodor control and removal agents, odor neutralizers, polymericdye transfer inhibiting agents, cationic deposition enhancing polymers,builders, heavy metal ion sequestrants, surfactants, suds stabilizingpolymers, pH modifiers, buffering agents, alkalinity sources, fabricsofteners, antistatic agents, dye fixatives, dye abrasion inhibitors,wrinkle reduction agents, wrinkle resistance agents, wrinkle releaseagents, silicones (e.g., silicone oils, cationic silicones, siliconegums, high refractive silicones, and silicone resins), soil releasepolymers, soil capture polymers, flocculating polymers, soil repellencyagents, colorants, pigments, opacifiers, adversive agents such asbittering agents, anti-redeposition agents, bleach activators, bleachcatalysts, bleach boosters, bleaches, photobleaches, enzymes, coenzymes,enzyme stabilizers, crystal growth inhibitors, anti-tarnishing agents,anti-oxidants, metal ion salts, corrosion inhibitors, antiperspirant,zinc pyrithione, plant derivatives, plant extracts, plant tissueextracts, plant seed extracts, plant oils, botanicals, botanicalextracts, essential oils, skin sensates, astringents, etc. (e.g., cloveoil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witchhazel distillate), anti-acne agents (salicylic acid), anti-dandruffagents, antifoaming agents, cosmetic astringents, cosmetic biocides,denaturants, drug astringents, external analgesics, film formers ormaterials, e.g., polymers, for aiding the film-forming properties andsubstantivity of the composition (e.g., copolymer of eicosene and vinylpyrrolidone), skin bleaching and lightening agents, (e.g., hydroquinone,kojic acid, ascorbic acid, magnesium ascorbyl phosphate, ascorbylglucoside, pyridoxine), skin-conditioning agents (e.g., humectants andocclusive agents), skin soothing and/or healing agents and derivatives(e.g., panthenol, and derivatives such as ethyl panthenol, aloe vera,pantothenic acid and its derivatives, allantoin, bisabolol, anddipotassium glycyrrhizinate), skin treating agents (e.g., vitamin Dcompounds, mono-, di-, and tri-terpenoids, beta-ionol, cedrol),sunscreen agents, insect repellants, oral care actives, personal healthcare actives, vitamins, anti-bacterial agents, anti-microbial agents,antifungal agents, their derivatives, and mixtures thereof.

In one embodiment, the benefit agent is at least partially surroundedwith a wall material to create a microcapsule. In one aspect, themicrocapsule wall material may comprise: melamine, polyacrylamide,silicones, silica, polystyrene, polyurea, polyurethanes, polyacrylatebased materials, gelatin, styrene malic anhydride, polyamides, andmixtures thereof. In one aspect, said melamine wall material maycomprise melamine crosslinked with formaldehyde,melamine-dimethoxyethanol crosslinked with formaldehyde, and mixturesthereof. In one aspect, said polystyrene wall material may comprisepolyestyrene cross-linked with divinylbenzene. In one aspect, saidpolyurea wall material may comprise urea crosslinked with formaldehyde,urea crosslinked with gluteraldehyde, and mixtures thereof. In oneaspect, said polyacrylate based materials may comprise polyacrylateformed from methylmethacrylate/dimethylaminomethyl methacrylate,polyacrylate formed from amine acrylate and/or methacrylate and strongacid, polyacrylate formed from carboxylic acid acrylate and/ormethacrylate monomer and strong base, polyacrylate formed from an amineacrylate and/or methacrylate monomer and a carboxylic acid acrylateand/or carboxylic acid methacrylate monomer, and mixtures thereof. Inone aspect, the perfume microcapsule may be coated with a depositionaid, a cationic polymer, a non-ionic polymer, an anionic polymer, ormixtures thereof. Suitable polymers may be selected from the groupconsisting of: polyvinylformaldehyde, partially hydroxylatedpolyvinylformaldehyde, polyvinylamine, polyethyleneimine, ethoxylatedpolyethyleneimine, polyvinylalcohol, polyacrylates, and combinationsthereof. In one aspect, one or more types of microcapsules, for exampletwo microcapsules types having different benefit agents may be used.

In one embodiment, the benefit agent is a perfume oil and may includematerials selected from the group consisting of3-(4-t-butylphenyl)-2-methyl propanal, 3-(4-t-butylphenyl)-propanal,3-(4-isopropylphenyl)-2-methylpropanal,3-(3,4-methylenedioxyphenyl)-2-methylpropanal, and2,6-dimethyl-5-heptenal, alpha-damascone, beta-damascone,delta-damascone, beta-damascenone,6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone,methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one,2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one,2-sec-butylcyclohexanone, and beta-dihydro ionone, linalool,ethyllinalool, tetrahydrolinalool, and dihydromyrcenol. Suitable perfumematerials can be obtained from Givaudan Corp. of Mount Olive, N.J., USA,International Flavors & Fragrances Corp. of South Brunswick, N.J., USA,or Quest Corp. of Naarden, Netherlands. In one aspect, the benefit agentis a perfume microcapsule.

In one embodiment, the benefit agent is encapsulated in a shell. In oneembodiment, the encapsulated benefit agent is perfume oil and the shellis a polymer.

In one embodiment, the benefit agent is a silicone. Useful silicones canbe any silicone comprising compound. In one embodiment, the siliconepolymer is selected from the group consisting of cyclic silicones,polydimethylsiloxanes, aminosilicones, cationic silicones, siliconepolyethers, silicone resins, silicone urethanes, and mixtures thereof.In one embodiment, the silicone is a polydialkylsilicone, alternativelya polydimethyl silicone (polydimethyl siloxane or “PDMS”), or aderivative thereof. In another embodiment, the silicone is chosen froman aminofunctional silicone, amino-polyether silicone, alkyloxylatedsilicone, cationic silicone, ethoxylated silicone, propoxylatedsilicone, ethoxylated/propoxylated silicone, quaternary silicone, orcombinations thereof.

In one embodiment the benefit agent is an enzyme. Suitable enzymesinclude proteases, amylases, cellulases, lipases, xylogucanases, pectatelyases, mannanases, bleaching enzymes, cutinases, and mixtures thereof.

For the enzymes, accession numbers or IDs shown in parentheses refer tothe entry numbers in the databases Genbank, EMBL and Swiss-Prot. For anymutations standard 1-letter amino acid codes are used witha*representing a deletion. Accession numbers prefixed with DSM refer tomicroorgansims deposited at Deutsche Sammlung von Mikroorganismen andZellkulturen GmbH, Mascheroder Weg 1b, 38124 Brunswick (DSMZ).

Protease.

The composition may comprise a protease. Suitable proteases includemetalloproteases and/or serine proteases, including neutral or alkalinemicrobial serine proteases, such as subtilisins (EC 3.4.21.62). Suitableproteases include those of animal, vegetable or microbial origin. In oneaspect, such suitable protease may be of microbial origin. The suitableproteases include chemically or genetically modified mutants of theaforementioned suitable proteases. In one aspect, the suitable proteasemay be a serine protease, such as an alkaline microbial protease or/anda trypsin-type protease. Examples of suitable neutral or alkalineproteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO),Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM),Bacillus pumilus (P07518) and Bacillus gibsonii (DSM14391).

(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.of porcine or bovine origin), including the Fusarium protease and thechymotrypsin proteases derived from Cellumonas (A2RQE2).

(c) metalloproteases, including those derived from Bacillusamyloliquefaciens (P06832, NPRE_BACAM).

Preferred proteases include those derived from Bacillus gibsonii orBacillus Lentus such as subtilisin 309 (P29600) and/or DSM 5483(P29599).

Suitable commercially available protease enzymes include: those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark);those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International; those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes; thoseavailable from Henkel/Kemira, namely BLAP (P29599 having the followingmutations S99D+S101 R+S103A+V104I+G159S), and variants thereof includingBLAP R(BLAP with S3T+V4I+V199M+V2051+L217D), BLAP X(BLAP withS3T+V4I+V2051) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V2051+L217D)all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin withmutations A230V+S256G+S259N) from Kao.

Amylase:

Suitable amylases are alpha-amylases, including those of bacterial orfungal origin. Chemically or genetically modified mutants (variants) areincluded. A preferred alkaline alpha-amylase is derived from a strain ofBacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens,Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp.,such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM9375, DSM 12368, DSMZ no. 12649, KSM AP1378, KSM K36 or KSM K38.Preferred amylases include:

(a) alpha-amylase derived from Bacillus licheniformis (P06278,AMY_BACLI), and variants thereof, especially the variants withsubstitutions in one or more of the following positions: 15, 23, 105,106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243,264, 304, 305, 391, 408, and 444.

(b) AA560 amylase (CBU30457, HD066534) and variants thereof, especiallythe variants with one or more substitutions in the following positions:26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,preferably that also contain the deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity with the wild-type enzymefrom Bacillus SP722 (CBU30453, HD066526), especially variants withdeletions in the 183 and 184 positions.

Suitable commercially available alpha-amylases are Duramyl®, Liquezyme®Termamyl®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, StainzymePlus®, Fungamyl® and BAN® (Novozymes A/S), Bioamylase® and variantsthereof (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges. m.b.H,Austria), Rapidase®, Purastar®, Optisize HT Plus®, Enzysize®, Powerase®and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM®(KAO, Japan). Preferred amylases are Natalase®, Stainzyme® and StainzymePlus®.

Cellulase:

The composition may comprise a cellulase. Suitable cellulases includethose of bacterial or fungal origin. Chemically modified or proteinengineered mutants are included. Suitable cellulases include cellulasesfrom the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia,Acremonium, e.g., the fungal cellulases produced from Humicola insolens,Myceliophthora thermophila and Fusarium oxysporum.

Commercially available cellulases include Celluzyme®, and Carezyme®(Novozymes A/S), Clazinase®, and Puradax HA® (Genencor InternationalInc.), and KAC-500(B)® (Kao Corporation).

In one aspect, the cellulase can include microbial-derivedendoglucanases exhibiting endo-beta-1,4-glucanase activity (E.C.3.2.1.4), including a bacterial polypeptide endogenous to a member ofthe genus Bacillus which has a sequence of at least 90%, 94%, 97% andeven 99% identity to the amino acid sequence SEQ ID NO:2 in U.S. Pat.No. 7,141,403) and mixtures thereof. Suitable endoglucanases are soldunder the tradenames Celluclean® and Whitezyme® (Novozymes A/S,Bagsvaerd, Denmark).

Preferably, the composition comprises a cleaning cellulase belonging toGlycosyl Hydrolase family 45 having a molecular weight of from 17 kDa to30 kDa, for example the endoglucanases sold under the tradenameBiotouch® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).

Highly preferred cellulases also exhibit xyloglucanase activity, such asWhitezyme®.

Lipase.

The composition may comprise a lipase. Suitable lipases include those ofbacterial or fungal origin. Chemically modified or protein engineeredmutants are included. Examples of useful lipases include lipases fromHumicola (synonym Thermomyces), e.g., from H. lanuginosa (T.lanuginosus), or from H. insolens, a Pseudomonas lipase, e.g., from P.alcaligenes or P. pseudoalcaligenes, P. cepacia, P. stutzeri, P.fluorescens, Pseudomonas sp. strain SD 705, P. wisconsinensis, aBacillus lipase, e.g., from B. subtilis, B. stearothermophilus or B.pumilus.

The lipase may be a “first cycle lipase”, preferably a variant of thewild-type lipase from Thermomyces lanuginosus comprising T231R and N233Rmutations. The wild-type sequence is the 269 amino acids (amino acids23-291) of the Swissprot accession number Swiss-Prot 059952 (derivedfrom Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipaseswould include those sold under the tradenames Lipex®, Lipolex® andLipoclean® by Novozymes, Bagsvaerd, Denmark.

Preferably, the composition comprises a variant of Thermomyceslanuginosa (059952) lipase having >90% identity with the wild type aminoacid and comprising substitution(s) at T231 and/or N233, preferablyT231R and/or N233R.

In another aspect, the composition comprises a variant of Thermomyceslanuginosa (059952) lipase having >90% identity with the wild type aminoacid and comprising substitution(s):

(a) S58A+V60S+I83T+A150G+L227G+T231R+N233R+I255A+P256K;

(b) S58A+V60S+I86V+A150G+L227G+T231R+N233R+I255A+P256K;

(c) S58A+V60S+I86V+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(d)S58A+V60S+I86V+T143S+A150G+G163K+S216P+L227G+T231R+N233R+I255A+P256K;

(e) E1*+S58A+V60S+I86V+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(f) S58A+V60S+I86V+K98I+E99K+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(g)E1N+S58A+V60S+I86V+K98I+E99K+T143S+A150G+L227G+T231R+N233R+I255A+P256K+L259F;

(h)S58A+V60S+I86V+K98I+E99K+D102A+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(i) N33Q+S58A+V60S+I86V+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(j)E1*+S58A+V60S+I86V+K98I+E99K+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(k)E1N+S58A+V60S+I86V+K98I+E99K+T143S+A150G+S216P+L227G+T231R+N233R+I255A+P256K;

(l) D27N+S58A+V60S+I86V+G91N+N94R+Dl UN+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(m)E1N+S58A+V60S+I86V+K98I+E99K+T143S+A150G+E210A+S216P+L227G+T231R+N233R+1255A+P256K;

(n) A150G+E210V+T231R+N233R+I255A+P256K; and

(o) I202L+E210G+T231R+N233R+I255A+P256K.

Xyloglucanase:

Suitable xyloglucanase enzymes have enzymatic activity towards bothxyloglucan and amorphous cellulose substrates, wherein the enzyme is aglycosyl hydrolase (GH) is selected from GH families 5, 12, 44 or 74.Preferably, the glycosyl hydrolase is selected from GH family 44.Suitable glycosyl hydrolases from GH family 44 are the XYG1006 glycosylhydrolase from Paenibacillus polyxyma (ATCC 832) and variants thereof.

Pectate Lyase:

Suitable pectate lyases are either wild-types or variants ofBacillus-derived pectate lyases (CAF05441, AAU25568) sold under thetradenames Pectawash®, Pectaway® and X-Pect® (from Novozymes A/S,Bagsvaerd, Denmark).

Mannanase:

Suitable mannanases are sold under the tradenames Mannaway® (fromNovozymes A/S, Bagsvaerd, Denmark), and Purabrite® (GenencorInternational Inc., Palo Alto, Calif.).

Bleaching Enzyme:

Suitable bleach enzymes include oxidoreductases, for example oxidasessuch as glucose, choline or carbohydrate oxidases, oxygenases,catalases, peroxidases, like halo-, chloro-, bromo-, lignin-, glucose-or manganese-peroxidases, dioxygenases or laccases (phenoloxidases,polyphenoloxidases). Suitable commercial products are sold under theGuardzyme® and Denilite® ranges from Novozymes. Advantageously,additional, preferably organic, particularly preferably aromaticcompounds are incorporated with the bleaching enzyme; these compoundsinteract with the bleaching enzyme to enhance the activity of theoxidoreductase (enhancer) or to facilitate the electron flow (mediator)between the oxidizing enzyme and the stain typically over stronglydifferent redox potentials.

Other suitable bleaching enzymes include perhydrolases, which catalysethe formation of peracids from an ester substrate and peroxygen source.Suitable perhydrolases include variants of the Mycobacterium smegmatisperhydrolase, variants of so-called CE-7 perhydrolases, and variants ofwild-type subtilisin Carlsberg possessing perhydrolase activity.

Cutinase:

Suitable cutinases are defined by E.C. Class 3.1.1.73, preferablydisplaying at least 90%, or 95%, or most preferably at least 98%identity with a wild-type derived from one of Fusarium solani,Pseudomonas Mendocina or Humicola Insolens.

Identity.

The relativity between two amino acid sequences is described by theparameter “identity”. For purposes of the present invention, thealignment of two amino acid sequences is determined by using the Needleprogram from the EMBOSS package (http://emboss.org) version 2.8.0. TheNeedle program implements the global alignment algorithm described inNeedleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. Thesubstitution matrix used is BLOSUM62, gap opening penalty is 10, and gapextension penalty is 0.5.

The water soluble shell may comprise a thermoplastic polymer capable ofsoftening with heat, flowing and hardening upon cooling. Examples ofwater soluble thermoplastic polymers include polyethers, polyesters,polyvinyl alcohols, polyoxazolines, polyureas, polyurathanes,thermoplastic starches and mixtures thereof.

Suitable polyethers may be selected from the group consisting ofpolyethylene glycol (PEG), polyethylene oxide, PEG copolymers, andmixtures thereof. Exemplary PEG homopolymers include: polyethyleneglycol available from Sigma Aldrich, CARBOWAX™ available from Dow, andPluriol® available from BASF. Exemplary PEG copolymers include Pluronic®available from BASF, polyetheramines available as Jeffamine® fromHuntsman Corporation, poly(lactide-block-ethylene glycol),poly(glycolide-block-ethylene glycol),poly(lactide-co-caprolactone)-block-poly(ethylene glycol), poly(ethyleneglycol-co-lactic acid), poly(ethylene glycol-co-glycolic acid),poly(ethylene glycol-co-poly(lactic acid-co-glycolic acid),poly(ethylene glycol-co-propylene glycol), poly(ethyleneoxide-block-propylene oxide-block-ethylene oxide), poly(propyleneoxide-block-ethylene glycol-block-propylene glycol), and poly(ethyleneglycol-co-caprolactone). The polymers may be linear, branched,cross-linked, dendritic, or star polymers. PEG copolymers may be random,block, comb, or graft copolymers.

In one embodiment, the PEG copolymer comprises at least about 50 wt. %PEG.

In one embodiment, at least one voxel of the set of voxels in the actualobject resulting from the translation, comprises a polyester derivedfrom the condensation reaction of a polyol, an ionic monomer andoptionally one or more chain extenders where the calculated chargedensity of the resulting polyester is 0.01 to 0.7 mEq/g, and mixturesthereof.

A polyol is a polymer comprising at least one, preferably two or morehydroxyl groups. Examples of polyols include poly(ethylene glycol),poly(ethylene oxide), poly(ethylene glycol) copolymers, andpoly(2-oxazoline). Examples of poly(2-oxazoline) polymers includepoly(2-ethyl-2oxazoline), poly(2-isopropyl-2-oxazoline),poly(2-propyl-2-oxazoline) andpoly[2-ethyl-2-oxazoline-co-2-(4-aminophenyl)-2-oxazoline].

Exemplary polyols include poly(ethylene glycol) available from SigmaAldrich, CARBOWAX™ available from Dow, and Pluriol® available from BASF.Exemplary polyethylene glycol copolymers include Pluronic® F127,Pluronic® F108, Pluronic® F68 and Pluronic® P105 available from BASF,poly(lactide-block-ethylene glycol), poly(glycolide-block-ethyleneglycol), poly(lactide-co-caprolactone)-block-poly(ethylene glycol),poly(ethylene glycol-co-lactic acid), poly(ethylene glycol-co-glycolicacid), poly(ethylene glycol-co-poly(lactic acid-co-glycolic acid),poly(ethylene glycol-co-propylene glycol), poly(ethyleneoxide-block-propylene oxide-block-ethylene oxide), poly(propyleneoxide-block-ethylene glycol-block-propylene glycol), and poly(ethyleneglycol-co-caprolactone).

In one embodiment, the PEG copolymer polyol comprises at least about 50wt. % PEG and having an average molecular weight of between about 2,000and about 100,000 AMU. Polyols may be linear, branched, cross-linked,dendritic or star polymers. Polyol copolymers may be random, block, combor graft copolymers.

Ionic monomers are molecules containing a cationic, anionic orzwitterionic moiety and at least two —COOR groups where R representsindependently hydrogen or a C1-C6 aliphatic chain. In one aspect, thecharged moiety is selected from the group consisting of —SO₃ ⁻, —SO₄ ⁻,PO₄ ⁻, PO₃ ⁻, —COO⁻ or —N(CH₃)₃ ⁺. The counterion may be organic orinorganic.

In another aspect, the ionic monomer has the following structure

whereR₁, R₂, R₃, R₄ and R₅ are independently —H, -C1-C6 alaphatic chain,—COOH or —COOCH₃n is an integer from 0 to 6X is −SO₃ ⁻, —SO₄ ⁻, PO₄ ⁻, PO₃ ⁻, —COO⁻ or —N(CH₃)₃ ⁺Y is a counter ion of opposite charge to X and chosen from Na⁺, K⁺, Li⁺,Ag⁺, ½ Ca⁺, ½ Mg⁺², ½ Zn⁺², ½ Mn⁺², ⅓ Al⁺³, F⁻, Cl⁻ or Br, CH₃SO₄—, orI⁻.wherein at least two of R₁, R₂, R₃, R₄ and R₅ are independently —COOCH₃or —COOH Preferred ionic monomers include salts of dimethyl5-sulfoisophthalate, sodium dimethyl 5-isophthalate, salts of dimethyl5-phosphoisophthalate, salts of quantized4-dimethylamino-benzene-1,2-dicarboxylic acid dimethyl ester, dimethylaminomalonate, DL-aspartic acid dimethyl ester hydrochloride, salts ofsulfo-dimethylfumarate, and dicarboxylic acid analogs to all listeddimethyl esters.

Chain extenders are molecules, oligomers or polymers comprising two ormore hydroxyl groups. Chain extenders may be anionic, cationic,zwitterionic or nonionic. Examples of suitable chain extenders includeethylene glycol, diethylene glycol, triethylene glycol, PEG200, salts ofPEG200-b-dimethyl 5-sulfoisophthalate-b-PEG200, cyclohexane dimethanol,butane diol, hexane diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol,cyclobutane diol, 2-Butene-1,4-diol, polycaprolactone diol,2-Dimethylamino-propane-1,3-diol, trans-2,3-Dibromo-2-butene-1,4-diol,1,4-Benzenedimethanol, salts of1,4-bis(2-hydroxyethoxy)-1,4-dioxobutane-2-sulfonate, divalent salts ofmono(hydroxyethyl) phthalate, divalent salts of mono(hydroxyehyoxyethyl)phthalate, divalent salts of mono(hydroxybutyl) hexolate,pentaerythritol, trimethylolpropane, and trimethylolethane.

The resulting polymer may be linear, branched or cross-linked. Ionexchange can be used to change the counter-ion of the polymer.

In one embodiment, the water-soluble polymer is polyvinyl alcohol orpolyvinyl alcohol copolymer. Examples of polyvinyl alcohol copolymersinclude butenediol vinylalcohol copolymers available as NichigoG-polymer™ from Nippon Gohsei and poly(vinyl alcohol)-co-poly(ethyleneglycol) available as Kollicoat® from BASF. The polyvinyl alcohols may bepartially or fully hydrolyzed.

In one embodiment, the water-soluble polymer is a polyoxazoline.Examples of polyoxazolines include poly(2-oxazoline) andpoly(2-ethyl-2-oxazoline) available as Aquazol from Polymer ChemistryInnovations, Inc.

The voxel may further comprise between about 0 and about 65 weightpercent (wt. %) of a filler, wherein the filler is a solid attemperatures greater than the melting, processing and printingtemperature of the overall composition. Fillers may be organic,inorganic or of mixed inorganic/organic nature. Suitable fillers areselected from the group consisting of: starches, gums, polysaccharides,proteins, amino acids, water soluble polymers, water degradablepolymers, water insoluble polymers, sugars, sugar alcohols, inorganicparticles, organic salts, surfactants, fatty amphiphiles and mixturesthereof.

Mixtures of fillers may be used. These mixtures can be physical blendsof two or more types of fillers or two or more fillers that are meltedor dissolved together to form a single filler comprising two or morematerials. Suitable methods for forming filler particles include anytypical method for creating powders such as grinding, milling, spraydrying, roll drying, and prilling.

Every dimension of the filler particles should be smaller than the FDMprinter nozzle diameter, more preferably less than 0.5 times and morepreferably less than 0.1 times the FDM printer nozzle diameter. The sizeof filler particles can be reduced by any common method for segregatingor reducing particle size including sieving, grinding, cryogenicgrinding, and milling Size and shape of the filler particles can bedetermined by common means such as sieving through a series of meshscreens or laser diffraction. In one embodiment, the filler particlesare spherical or ellipsoidal in shape. Exemplary filler particles arespherical in shape.

The melting temperature of the filler particle must be greater than themelting, processing and printing temperatures of the final mixture.Melting temperature of the filler particles may be determined throughstandard methods including differential scanning calorimetry or a meltpoint apparatus.

The composition may further comprise 0 to 35 percent by weight of aplasticizing agent. Some examples of suitable plasticizing agentsinclude water, polyethylene glycol with a molecular weight of 1,000g/mol or lower, ethylene glycol, propylene glycol, diethylene glycol,and glycerin.

In one embodiment, the water soluble shell encloses a plurality ofvolumes. The plurality of volumes may be arranged in association withthe needs of the product designer and according to the nature of theactive element contained within each of the respective volumes.Exemplary arrangements include, stacked volumes, nested volumes,adjacent volumes and combinations thereof.

In one embodiment, both the active agent in the container and the shellcontain one or more benefit agents. Selecting different wall thicknessesand changing the concentration of benefit agent on a voxel by voxelbasis enables controlled release profile of benefit agents contained inthe shell. Benefit agents contained in the enclosed volume allow for aburst release once water compromises the integrity of the containerexposing the contents to water. This burst release is not possible withbenefit agents located within voxels. The combination of benefit agentsin the active agent and the voxels of the container allow for controlledand burst release. Additionally, benefit agents that negatively interactwith other ingredients can be segregated either in the active agent orat least on voxel.

In one embodiment, the active element contains less than 40 wt. % water.More preferably, the active element contains less than 10 wt. % water.

In one embodiment, the container, active element and benefit agent arechosen to form a consumer goods product. In one embodiment, thethree-dimensional object is a consumer products. Examples of consumerproducts include, articles, baby care, beauty care, fabric & home care,family care, feminine care, products or devices intended to be used orconsumed in the form in which it is sold, and is not intended forsubsequent commercial manufacture or modification. Such products includebut are not limited to fabric softener, fabric enhancer, laundryadditive, conditioners, hair colorants, body wash, shampoo, facial wash,dish detergent, and heavy duty laundry detergent products for and/ormethods relating to treating hair (human, dog, and/or cat), includingbleaching, coloring, dyeing, conditioning, shampooing, styling; personalcleansing; cosmetics; skin care including application of creams,lotions, and other topically applied products for consumer use; andshaving products, products for and/or methods relating to treatingfabrics, hard surfaces and any other surfaces in the area of fabric andhome care, including: air care, car care, dishwashing, fabricconditioning (including softening), laundry detergency, laundry andrinse additive and/or care, hard surface cleaning and/or treatment, andother cleaning for consumer or institutional use; and waterpurification. In one embodiment, the container is intended to be fullydissolved in water for a single use. In another embodiment, thecontainer slowly erodes allowing for multiple uses.

In one embodiment, a multicompartment container may be filled withparticular formulated compositions in each of the multitude of chambersor compartments. Multi-compartment containers may contain a plurality ofbenefit agents. By way of a non-limiting example, a two- orthree-component container may contain the formulations presented inTable 1 in separate compartments, where dosage is the amount of theformulation in the respective enclosure. At least one of thecompartments contains a liquid composition. Any of the compositions inany of the compartments below may be present in any combination in apouch, or may even be individually presented. e.g., in amono-compartment container

TABLE 1 G H I 3 compartments 2 compartments 3 compartments Compartment #1 2 3 1 2 1 2 3 Dosage (g) 34.0 3.5 3.5 30.0 5.0 25.0 1.5 4.0Ingredients Weight % Alkylbenzene sulfonic acid 20.0 20.0 20.0 10.0 20.020.0 Alkyl sulfate 2.0 C12-14 alkyl 7-ethoxylate 17.0 17.0 17.0 17.017.0 Cationic surfactant 1.0 Zeolite A 10.0 C12-18 Fatty acid 13.0 13.013.0 18.0 18.0 Sodium acetate 4.0 enzymes 0-3 0-3 0-3 0-3 0-3 SodiumPercarbonate 11.0 TAED 4.0 Organic catalyst ¹ 1.0 PAP granule ² 50Polycarboxylate 1.0 Polyethyleneimine ethoxylate ³ 2.2 2.2 2.2Hydroxyethane diphosphonic acid 0.6 0.6 0.6 0.5 Ethylene diaminetetra(methylene 0.4 phosphonic) acid Brightener 0.2 0.2 0.2 0.3 0.3Mineral oil Hueing dye ⁴ 0.05 0.035 0.12 Perfume 1.7 1.7 0.6 1.5 Waterand minors (antioxidant, 10.0 10.0 10.0 4.0 aesthetics, . . .) Buffers(sodium To pH 8.0 for liquids carbonate, monoethanolamine) ⁵ To RA > 5.0for powders Solvents (1,2 propanediol, To 100% ethanol) for liquids,sodium sulfate for powders ¹ Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl]esteras described in U.S. Pat. No. 7,169,744 ² PAP =Phtaloyl-Amino-Peroxycaproic acid, as a 70% active wet cake ³Polyethylenimine (MW = 600) with 20 ethoxylate groups per —NH. ⁴Ethoxylated thiophene, EO (R₁ + R₂) = 5 ⁵ RA = Reserve Alkalinity (gNaOH/dose)

Example 1—Processes for Synthesizing poly(PEG8k-co-NaSIP)

This non-limiting example illustrates the preparation of apoly(PEG8k-co-NaSIP) synthesized via melt transesterification. The meltpolymerization of components was prepared by mixing together:

200.01 g of PEG 8,000

7.40 g of dimethyl 5-sulfoisophthalate219.5 mg of sodium acetate (NaOAc)103.7 mg of Ti(OiPr)₄ (100 mg/mL in n-butanol)

The components are subjected to 3 vacuum purge cycles to remove air. Thecomponents are melted together by placing in a silicone oil bath heatedto 170° C. under a nitrogen flow. After the components are fully melted,vacuum was applied to 0.2 mbar and allowed to polymerize for 2-4 hours.The reaction mixture is cooled under nitrogen flow.

Example 2—Processes for Synthesizing poly(PEG8k-co-CaSIP) Filament

This non-limiting example illustrates the preparation of apoly(PEG8k-co-CaSIP) synthesized via melt transesterification. The meltpolymerization of components was prepared by mixing together:

200.01 g of PEG 8,000

7.40 g of dimethyl 5-sulfoisophthalate219.5 mg of sodium acetate (NaOAc)103.7 mg of Ti(OiPr)₄ (100 mg/mL in n-butanol)

The components are subjected to 3 vacuum purge cycles to remove air. Thecomponents are melted together by placing in a silicone oil bath heatedto 170° C. under a nitrogen flow. After the components are fully melted,vacuum was applied to 0.2 mbar and allowed to polymerize for 2-4 hours.The reaction mixture is cooled under nitrogen flow. The resultingpolymer is poly(PEG8k-co-NaSIP).

Ion-exchanged is used to create poly(PEG8k-co-CaSIP) frompoly(PEG8k-co-NaSIP). The dialysis procedure is begun by dissolving31.51 g poly(PEG8k-co-NaSIP) in 315.1 mL DI H₂O. To the polymersolution, 2.3967 g of CaCl₂ is added and the polymer solution is placedinto cellulose dialysis membranes (molecular weight cutoff=3,500 g/mol)and placed into 20 L of DI H₂O. On days 2 and 3, 2.2659 g and 2.3838 gCaCl₂) are added to the polymer solution and the water is replaced. Ondays 4, 5, and 6, the water is replaced. The resulting ion-exchangedpolymer solution is frozen and lyophilized to remove residual water.

Poly(PEG8k-co-CaSIP) filament is created using a desktop scale singlescrew extruder set to a temperature of 70 C. The polymer is dried usinga vacuum oven and cut into to approximately 0.2 mm pellets for theextruder hopper. A conveyor belt is used to pull the filament to adiameter of 1.75 mm from a 2 mm diameter die. Forced convection is usedalong the conveyor belt and the extruder hopper. Finished filament isstored with desiccant or in a desiccator before use.

Example 3—Single Liquid Detergent Filled Gem Containers

Gems shapes were FDM printed using a direct drive system with an allmetal hot end with a 0.4 mm diameter nozzle. For 1.8 mmpoly(PEG8k-co-CaSIP) filament, the printing temperature was 70° C. usinga glass bed heated to 40° C. For 1.8 mm polyvinyl alcohol filament, soldunder the trade name Mowiflex, the printing temperature was 190 to 215 Cusing a glass bed heated to 50 to 70 C. Surface treatment or adhering amaterial with sufficient surface roughness to the glass is used toimprove first layer adhesion. Forced convection is used to improve partquality of small features. The print was paused before the last fewlayers were complete and a syringe used to fill the shape with liquid(40 wt. % water) and low-water (10 wt. % water) liquid detergent. Afterfilling, the print was resumed and the shape finished completely sealingthe container.

Example 4—Dual Liquid Detergent Filled Container

Shapes were printed FDM printed using a direct drive system with an allmetal hot end with a 0.4 mm diameter nozzle. For 1.8 mmpoly(PEG8k-co-CaSIP) filament, the printing temperature was 70° C. usinga glass bed heated to 40° C. Surface treatment or adhering a materialwith sufficient surface roughness to the glass is used to improve firstlayer adhesion. Forced convection is used to improve part quality ofsmall features. The print was paused before the last few layers werecomplete and a syringe used to fill each cavity with a different liquiddetergent formulation. The wall thickness of one cavity was 0.6 mm andthe other 0.9 mm After filling, the print was resumed and the shapefinished completely sealing the container.

Example 5—Branded Dual Liquid Filled Container

Shapes according to Figure X3 were printed FDM printed using a directdrive system with an all metal hot end with a 0.4 mm diameter nozzle.For 1.8 mm poly(PEG8k-co-CaSIP) filament, the printing temperature was70° C. using a glass bed heated to 40° C. Surface treatment or adheringa material with sufficient surface roughness to the glass is used toimprove first layer adhesion. Forced convection is used to improve partquality of small features. The print was paused before the last fewlayers were complete and a syringe used to fill each cavity with adifferent liquid detergent formulation. After filling, the print wasresumed and the shape finished completely sealing the container.

Example 6—Powder Filled Container

Shapes according to Figure X4 were printed FDM printed using a directdrive system with an all metal hot end with a 0.4 mm diameter nozzle.For 1.8 mm poly(PEG8k-co-CaSIP) filament, the printing temperature was70° C. using a glass bed heated to 40° C. Surface treatment or adheringa material with sufficient surface roughness to the glass is used toimprove first layer adhesion. Forced convection is used to improve partquality of small features. The print was paused before the last fewlayers were complete and a powder detergent composition added to cavity.After filling, the print was resumed and the shape finished completelysealing the container.

Example 7—Dual Liquid and Powder Detergent Stacked Container

Shapes according to Figure X5 were printed FDM printed using a directdrive system with an all metal hot end with a 0.4 mm diameter nozzle.For 1.8 mm poly(PEG8k-co-CaSIP) filament, the printing temperature was70° C. using a glass bed heated to 40° C. Surface treatment or adheringa material with sufficient surface roughness to the glass is used toimprove first layer adhesion. Forced convection is used to improve partquality of small features. The print was paused before the last fewlayers were complete of the lower void and a powder detergentcomposition added to cavity. The print was resumed, sealing the firstchamber. The print was paused a second time a and the top void filledwith a liquid detergent composition. After the second filling, the printwas resumed and the shape finished completely sealing the container.

Example 8—Helical Shaped, Dual Liquid Filled Container

Helical shaped containers may be printed FDM printed using a directdrive system with an all metal hot end with a 0.4 mm diameter nozzle.For 1.8 mm polyvinyl alcohol filament, sold under the trade nameMowiflex, the printing temperature was 195 C using a glass bed heated to60 C. Surface treatment or adhering a material with sufficient surfaceroughness to the glass is used to improve first layer adhesion. Forcedconvection is used to improve part quality of small features. The printwas paused before the last few layers were complete and a syringe usedto fill the cavities with two different liquid detergent compositions inan alternating pattern. After filling, the print was resumed and theshape finished completely sealing the container.

Results

Liquid detergent filled gems according to Example 3 were printed usingtwo materials, poly(PEG8k-co-CaSIP) and polyvinyl alcohol and three wallthicknesses. Each gem was placed in deionized water with mild agitationand observed visually. The water became visually turbid when thecontainer released the detergent composition. The time to release thedetergent composition can be controlled by changing both the wallmaterial type and thickness.

TABLE 2 Time to release liquid detergent composition from gem in Example2 when placed in deionized water when made with varying wall materialand thickness. Wall Thickness Wall Material 0.6 mm 0.9 mm 1.2 mmPolyvinyl alcohol 15 min 36 min 60 min Poly(PEG-co-CaSIP)  7 min 20 min41 minPrinted containers were stored in the laboratory without temperature orhumidity control. The observed stability of these containers is listedin Table 2.

TABLE 3 Stability results for containers stored at ambient laboratorytemperatures between 20 and 25 C. Samples are considered unstable whenthey show visual leaking. Shape Wall thickness Polymer Fill StabilityResults Example 3 0.6 mm Poly(PEG8k- Low water 6+ months co-CaSIP)detergent Example 3 0.6 mm Poly(PEG8k- Liquid 1 hour co-CaSIP) detergentExample 8 TBD Polyvinyl Low water 2+ years alcohol detergentLiquid filled gems of Example 3 were placed for detailed six-monthstability testing. Table 3 illustrates the stability results for avariety of temperature and humidity storage conditions.

TABLE 4 Stability results for containers stored at temperatures 5 and 40C. Capsule % Volatile Visual Storage Strength Fluid loss Leakage of TempOpen/Closed after Six after six Fluid from (° C.) Container Monthsmonths container  5 Closed Similar to 11 No 20 Open original 14 No gems.25 Closed No fracture 15 No 30° C./65% RH Open when 14 No 40 Closedsqueezed by 17 Slight at tip hand .

FIG. 1 provides a perspective illustration of the exterior of oneembodiment of the invention. FIG. 2 provides a cross-sectional view ofthe interior of the container of FIG. 1. As shown in FIG. 2, thecontainer 1000 comprises shell members 100 which define and separatedistinct volumes. The figure illustrates stacked and nested volumes aswell as volumes containing filling materials 200, 300, and 400.

Combinations:

-   -   A. A water soluble container comprising a water soluble shell        enclosing a volume, the shell at least partially comprising a        set of voxels.    -   B. The water soluble container according to paragraph A wherein        the enclosed volume is at least partially filled with an active        element.    -   C. The water soluble container according to paragraph B wherein        the active element comprises a solid element.    -   D. The water soluble container according to any of paragraphs        B-C wherein the active element comprises a liquid element.    -   E. The water soluble container according to any of paragraphs        B-D wherein the active element comprises a gaseous element.    -   F. The water soluble container according to any of paragraphs        B-E wherein the active agent is selected from the group        consisting of: personal cleansing and/or conditioning agents        such as hair care agents such as shampoo agents and/or hair        colorant agents, hair conditioning agents, skin care agents,        sunscreen agents, and skin conditioning agents; laundry care        and/or conditioning agents such as fabric care agents, fabric        conditioning agents, fabric softening agents, fabric        anti-wrinkling agents, fabric care anti-static agents, fabric        care stain removal agents, soil release agents, dispersing        agents, suds suppressing agents, suds boosting agents, anti-foam        agents, and fabric refreshing agents; hard surface care agents,        and/or conditioning agents such as liquid and/or powder        dishwashing agents (for hand dishwashing and/or automatic        dishwashing machine applications), and polishing agents; other        cleaning and/or conditioning agents such as antimicrobial        agents, perfume, bleaching agents (such as oxygen bleaching        agents, hydrogen peroxide, percarbonate bleaching agents,        perborate bleaching agents, chlorine bleaching agents), bleach        activating agents, chelating agents, builders, lotions,        brightening agents, air care agents, carpet care agents,        water-softening agents, water-hardening agents, pH adjusting        agents, enzymes, flocculating agents, effervescent agents,        preservatives, cosmetic agents, make-up removal agents,        lathering agents, deposition aid agents, coacervate-forming        agents, clays, thickening agents, latexes, silicas, drying        agents, odor control agents, antiperspirant agents, cooling        agents, warming agents, absorbent gel agents, anti-inflammatory        agents, dyes, pigments, acids, and bases; liquid treatment        active agents; agricultural active agents; industrial active        agents; water-treatment agents such as water clarifying and/or        water disinfecting agents, and combinations thereof.    -   G. The water soluble container according to any of paragraphs        A-F wherein the water soluble shell encloses a plurality of        volumes.    -   H. The water soluble container according to paragraph G wherein        the plurality of volumes comprises a set of nested volumes.    -   I. The water soluble container according to any of paragraphs        G-H wherein the plurality of volumes comprises a set of stacked        volumes.    -   J. The water soluble container according to any of paragraphs        A-I wherein the water soluble shell comprises a benefit agent.    -   K. The water soluble container according to paragraph J wherein        the benefit agent is selected from the group consisting of:        perfumes, pro-perfumes, finishing aids, malodor control and        removal agents, odor neutralizers, polymeric dye transfer        inhibiting agents, cationic deposition enhancing polymers,        builders, heavy metal ion sequestrants, surfactants, suds        stabilizing polymers, pH modifiers, buffering agents, alkalinity        sources, fabric softeners, antistatic agents, dye fixatives, dye        abrasion inhibitors, wrinkle reduction agents, wrinkle        resistance agents, wrinkle release agents, silicones (e.g.,        silicone oils, cationic silicones, silicone gums, high        refractive silicones, and silicone resins), soil release        polymers, soil capture polymers, flocculating polymers, soil        repellency agents, colorants, pigments, opacifiers, adversive        agents such as bittering agents, anti-redeposition agents,        bleach activators, bleach catalysts, bleach boosters, bleaches,        photobleaches, enzymes, coenzymes, enzyme stabilizers, crystal        growth inhibitors, anti-tarnishing agents, anti-oxidants, metal        ion salts, corrosion inhibitors, antiperspirant, zinc        pyrithione, plant derivatives, plant extracts, plant tissue        extracts, plant seed extracts, plant oils, botanicals, botanical        extracts, essential oils, skin sensates, astringents, etc.        (e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol,        menthyl lactate, witch hazel distillate), anti-acne agents        (salicylic acid), anti-dandruff agents, antifoaming agents,        cosmetic astringents, cosmetic biocides, denaturants, drug        astringents, external analgesics, film formers or materials,        e.g., polymers, for aiding the film-forming properties and        substantivity of the composition (e.g., copolymer of eicosene        and vinyl pyrrolidone), skin bleaching and lightening agents,        (e.g., hydroquinone, kojic acid, ascorbic acid, magnesium        ascorbyl phosphate, ascorbyl glucoside, pyridoxine),        skin-conditioning agents (e.g., humectants and occlusive        agents), skin soothing and/or healing agents and derivatives        (e.g., panthenol, and derivatives such as ethyl panthenol, aloe        vera, pantothenic acid and its derivatives, allantoin,        bisabolol, and dipotassium glycyrrhizinate), skin treating        agents (e.g., vitamin D compounds, mono-, di-, and        tri-terpenoids, beta-ionol, cedrol), sunscreen agents, insect        repellants, oral care actives, personal health care actives,        vitamins, anti-bacterial agents, anti-microbial agents,        antifungal agents, their derivatives, and mixtures thereof.    -   L. The water soluble container according to any of paragraphs        A-K wherein at least one voxel comprises a water soluble polymer        selected form the group consisting of polyethers, polyesters,        polyvinyl alcohols, polyoxazolines, polyureas, polyurathanes,        thermoplastic starches and mixtures thereof    -   M. The water soluble container according to paragraph L wherein        the water soluble polymer is selected form the group consisting        of polyethylene glycol, polyethylene oxide, Pluronics,        polyethylene oxide copolymers, polyvinyl alcohol, polyvinyl        alcohol copolymers, butenediol vinylalcohol copolymers,        poly(2-ethyl-2-oxazoline), polyesters with a charge density of        0.01 to 0.7 mEq/g and combinations thereof.    -   N. The water soluble container according to any of paragraphs        A-M wherein at least one voxel of the shell comprises a        plasticizer and/or a filler.    -   O. The water soluble container according to any of paragraphs        A-N wherein the active element comprises between 0 and 40 weight        percent water.    -   P. The water soluble container according to paragraph 0 wherein        the active element comprises between 0.0001 and 20 wt. % water.    -   Q. The water soluble container according to paragraph P wherein        the active element comprises between 0.001 and 10 wt. % water    -   R. The water soluble container according to any of paragraphs        A-Q wherein the shell is comprised solely of voxels.    -   S. The water soluble container according to any of paragraphs        B-R where the container is a consumer goods product.    -   T. A method for creating a water soluble container comprising        the steps of:        -   a. creating a digital representation of the container as a            set of voxels;        -   b. printing a portion of the voxels to create a void space            partially surrounded by voxels;        -   c. filling some or all of the void space with an active            element; and        -   d. printing the remaining voxels to fully enclose the active            element.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A consumer product comprising: a. a water-solubleshell comprising a set of voxels; wherein the shell encloses a volume;b. a solid element comprising a benefit agent; wherein the enclosedvolume is at least partially filled with the solid element; wherein theshell fully encloses the solid element.
 2. The product of claim 1,wherein the consumer product fully dissolves in water for a single use.3. The product of claim 1, wherein the solid element comprises a powder.4. The product of claim 1, wherein the product is stable for six monthsor more.
 5. The product of claim 1, wherein the shell is comprisedsolely of the set of voxels.
 6. The product of claim 1, wherein theshell comprises a thickness wherein the thickness varies across thevolume.
 7. The product of claim 1, wherein the shell further comprises asecond benefit agent wherein the second benefit agent is releasable whenthe shell is solubilized.
 8. The product of claim 1, wherein the set ofvoxels comprise a water-soluble polymer selected form the groupconsisting of polyethers, polyesters, polyvinyl alcohols,polyoxazolines, polyureas, polyurathanes, thermoplastic starches andmixtures thereof.
 9. The product of claim 1, wherein the set of voxelscomprise a water-soluble polymer selected from the group consisting ofpolyethylene glycol, polyethylene oxide, polyethylene glycol copolymers,polyethylene oxide copolymers, polyvinyl alcohol, polyvinyl alcoholcopolymers, butenediol vinylalcohol copolymers,poly(2-ethyl-2-oxazoline), and combinations thereof.
 10. The product ofclaim 1, wherein the set of voxels comprises a plasticizer.
 11. Theproduct of claim 1, wherein the set of voxels further comprise a secondbenefit agent wherein the second benefit agent is the same or differentthan the first benefit agent.
 12. The product of claim 1, wherein theconsumer product is selected from the group consisting of fabricsoftener, fabric enhancer, laundry additive, hair conditioner, bodywash, hair shampoo, facial wash, dish detergent, laundry detergent, hairstyling product, personal cleansing product, cream, lotion, shavingproduct, hard surfaces cleaner, air care product, product, car care,dishwashing, and combinations thereof.
 13. The product of claim 1,wherein the benefit agent is selected from the group consisting ofperfumes, pro-perfumes, finishing aids, malodor control and removalagents, odor neutralizers, polymeric dye transfer inhibiting agents,cationic deposition enhancing polymers, builders, heavy metal ionsequestrants, surfactants, suds stabilizing polymers, pH modifiers,buffering agents, alkalinity sources, fabric softeners, antistaticagents, dye fixatives, dye abrasion inhibitors, wrinkle reductionagents, wrinkle resistance agents, wrinkle release agents, siliconessoil release polymers, soil capture polymers, flocculating polymers,soil repellency agents, colorants, pigments, opacifiers, adversiveagents, anti-redeposition agents, bleach activators, bleach catalysts,bleach boosters, bleaches, photobleaches, enzymes, coenzymes, enzymestabilizers, crystal growth inhibitors, anti-tarnishing agents,anti-oxidants, metal ion salts, corrosion inhibitors, antiperspirant,zinc pyrithione, plant derivatives, plant extracts, plant tissueextracts, plant seed extracts, plant oils, botanicals, botanicalextracts, essential oils, skin sensates, astringents, etc. anti-acneagents, anti-dandruff agents, antifoaming agents, cosmetic astringents,cosmetic biocides, denaturants, drug astringents, external analgesics,film formers, skin bleaching and lightening agents, skin-conditioningagents, skin soothing agents, skin healing agents and derivatives, skintreating agents, sunscreen agents, insect repellants, oral care actives,personal health care actives, vitamins, anti-bacterial agents,anti-microbial agents, antifungal agents, and mixtures thereof.
 14. Theproduct of claim 1, wherein the product comprises two or morecompartments.
 15. A consumer product comprising: a. a water-solubleshell comprising a set of voxels comprising a water-soluble polymer;wherein the shell encloses a volume; b. a solid element comprising asurfactant; wherein the enclosed volume is at least partially filledwith the solid element; wherein the shell fully encloses the solidelement.
 16. The product of claim 15, further wherein the liquid elementfurther comprises a filler selected from the group consisting ofstarches, gums, polysaccharides, proteins, amino acids, water solublepolymers, water degradable polymers, water insoluble polymers, sugars,sugar alcohols, inorganic particles, organic salts, surfactants, fattyamphiphiles and mixtures thereof.
 17. The product of claim 15, whereinthe solid element comprises a powder.
 18. The product of claim 15,wherein the product is a laundry detergent or shampoo.
 19. The productof claim 15, further comprising a second benefit agent selected from thegroup consisting of bleaching agents, chelating agents, perfumes, andcombinations thereof.
 20. The product of claim 15, wherein the shell iscomprised solely of the set of voxels.